Codex @codex  0

An allene contains the unit $\mathrm{C}=\mathrm{C}=\mathrm{C}$ with two consecutive carbon–carbon covalent bonds of order two. Suitable terminal substituents give axial chirality.

An allene has a $\mathrm{C}=\mathrm{C}=\mathrm{C}$ unit whose terminal substituents lie in perpendicular planes. In $\mathrm{abC}=\mathrm{C}=\mathrm{Ccd}$, with $a\ne b$ and $c\ne d$, the two terminal pairs can define enantiomers without any tetrahedral carbon stereocenter. The groups need be different within each end pair, not all four mutually different. This is axial chirality.^[ref]

Chirality means that a molecule cannot be superposed on its mirror image. A carbon attached to four different groups is a common source of chirality; the definition concerns the whole molecule, rather than requiring this particular structural feature.

The test is spatial: apply a translation and a rotation to the entire molecule until corresponding chemical atoms coincide, keeping their identities and chemical bonds. A mirror operation is a reflection; physically turning a model is a rotation. They are different operations. If no such superposition exists, the two forms are enantiomers; if one succeeds, the molecule is achiral. A different-looking flat drawing alone establishes neither conclusion.

For a simple molecule with exactly one tetrahedral stereocenter and four constitutionally different substituents, the mirror forms cannot superpose. Compare entire attached groups, including paths around a ring, rather than just the first chemical atom. Several tetrahedral stereocenters require a whole-molecule check: a meso compound can be achiral. Conversely, axial chirality needs no tetrahedral stereocenter.^[ref]

Why care about this distinction? Two enantiomers can fit differently into an already chiral molecule, just as two opposite hands fit differently into one glove. Thus a protein's spatial arrangement can distinguish a mirror pair even when an achiral measurement cannot. Polarimetry provides a different kind of test: it measures a sample's net optical rotation, which depends on the populations of its enantiomers.

For a tetrahedral stereocenter, rank its four substituents using stereochemical sequence rules. With lowest-priority group pointing away, a clockwise $1\to 2\to 3$ sequence is $R$ and a counterclockwise sequence is $S$. Looking from the other side reverses the apparent sequence, so the viewing condition is essential. The geometric letters A/B/C/D in the tetrahedral mirror-image test carry no assigned priority. Neither $R$ nor $S$ determines positive or negative optical rotation.^[ref]

Stereochemical sequence rules rank substituents for R and S configuration. Compare the directly attached chemical atoms by atomic number first, then resolve ties by comparing successive shells at the first difference. Isotopes and multiple chemical bonds require additional rules. This ranking convention does not involve optical rotation.^[ref]

A substituent is an attached chemical atom or group considered relative to a chosen molecular framework. Testing whether two substituents are identical may require comparing their full chemical bond connectivity and stereochemistry.

Take a central chemical atom at the origin and four substituents at the vertices of an ideal regular tetrahedron:These dimensionless coordinates describe shape, not measured bond lengths. For distinct labels A, B, C and D, define a signed determinantIt is six times the oriented volume of the labelled tetrahedron. A translation cancels from the differences. A rotation $Q$ has $\det Q=+1$ and preserves $\Delta$, whereas the mirror matrix $S=\mathrm{diag}(-1,1,1)$ has $\det S=-1$ and changes it to $-16$. Consequently no rotation can place every distinct label on its mirror partner. This argument uses three-dimensional coordinates, not clockwise order on a page.

Now let C and D both be the same substituent H. Swapping these identical groups is allowed. For this model the half-turnabout the axis $(0,1,1)$ maps the reflected A and B to their original positions and exchanges the two H positions. The models superpose. With distinct C and D, the same half-turn fails precisely at those two labels; the determinant argument rules out every other rotation as well. This is the local reason two identical hydrogen chemical atoms prevent glycine's amino acid alpha carbon from being a tetrahedral stereocenter.

For a flexible molecule, also distinguish conformational isomerism from a persistent enantiomer pair. A particular frozen shape may be chiral while ordinary internal motions interconvert mirror shapes. Turning the entire model is always allowed in a spatial comparison; an internal motion must be considered with its actual accessibility and timescale.